A STUDY  OF  THE  PROPERTIES  OF  THE 
EXTRACT  OBTAINED  FROM  A CAN- 
NED COAL  USEING  BENZENE  AND 
XYLENE  AS  SOLVENTS 

BY 

PERRY  ROBERT  WILSON 


THESIS 

FOR  THE 

DEGREE  OF  BACHELOR  OF  SCIENCE 


GFIEMIGAL  ENGINEERING 


GOLLEGE  OF  LIBERAL  ARTS  AND  SCIENGES 

UNIVERSITY  OF  ILLINOIS 


1922 


5C02HH 


Digitized  by  the  Internet  Archive 
in  2016 


https://archive.org/details/studyofpropertieOOwils 


Acknowledgement 

The  writer  wishes  to  express  his  thanks  and  appreciation 

to  Doctor  Layng* 


Index 


Introduction  

The  Extraction  of  a Cannel  Coal . Intriducjsion  3 

Purpose  4 

Experimental  5 

conclusions  9 

A Study  of  the  Extract  Obtained  from  a Cannel  Coal  ....10 

Purpose  12 

Methods  of  Investigation 13 

Experimental  15 

Conclusions  17 

Conclusions  from  entire  work  18 


1 


A STUDY  OF  TI-IF  ^^ROPFRTIFS  OF  THE  EXTRACT  OBTAINED  FROM  A 
CAMEL  COAL  USEING  BENZENE  AND  XYLENE  AS  SOLVENTS. 

Introduction. 

pannel  coal  has  been  classed  with  coals  because  of  the 
proximate  and  ultimate  analysis. gut  because  cannel  coals  have  a 
different  structure  and  their  products  on  carbonization  are 
different  from  those  ©f  coal, it  has  been  suggested  that  they  be 

classed  rather  as  bitumens. 

8 

Theissen  has  made  a microscopic  examination  of  cannel  coal, 
and  found  that  resin,pollin,and  spores  fonned  the  main  biilk  of  the 
coal. He  admits  that  although  almost  all  of  the  Ingreidients  present 
in  a bituminous  coal, are  present  in  a cannel  coal, but  that  the  pro- 
portions are  so  different, that  the  cannel  coal  should  not  be 
classed  as  a true  coal. 

As  to  the  other  methods  of  investigation  of  the  constitution 
of  coal, no  one  has  investigated  from  a solvent  point  of  view. 
Solvent  action  and  an  examination  of  the  extract  should  yield  some 
valuable  evidence  toward  the  classification  of  cannel  coal. 

The  purpose  of  this  investigation  is, therefore, to  attempt  to 
classify  a cannel  coal, by  studying  the  extract  obtained  from  it, 
useing  benzene  and  xylene  as  solvents. 


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3 


Part  !• 

Tbe  Bxtraction  of  a Oannel  Coal  Useing  Benzene  and  Xylene 

as  Solvents. 

I .Introduction. 

Solvent  action  is  a good  way  to  study  ooal  or  a similar  sub- 
stance since  it  will  remove  a jjart  of  the  substance  in  its  ori- 
ginal form  and  not  attack  the  tther  portion. The  first  line  of 
investigation  should  consist  of  a study  of  solvents, in  order  to 
determine  tbe  one  which  will  seperate  the  material  into  two  dis- 
tinct portions, and  give  a maximum  extraction. 

Many  investigations  have  been  taken  up  in  order  to  find  such 

1 

a suitable  solvent. J. A. Bmythe  of  Gottigen  was  one  of  the  first 

solvent  workers, useing  benzene, chloroform, ethyl  alcohol, light 

petroleum, and  ace tone. However  he  was  only  able  to  obtain  an  ex- 

1 

traction  of  three  percent. Bedson  and  Garrick  tried  pyridine  and 

obtained  as  much  as  twenty  percent  extraction, from  a Durham  coal. 

1 

Wheeler  and  his  co-workers  also  used  pyridine . They  found  that 

pyridine  took  out  the  material  which  is  responsible  for  the  coking 

of  coal, and  termed  the  extracted  material  the  resinic  constituent 
1 

of  coal. Wahl  used  pyridine  under  pressure, that  is  sealed  in  a glass 
tube, and  was  able  to  obtain  an  extraction  of  over  forty  percent. 

He  explained  this  by  saying  that  the  pyridine  acted  as  a depolmer 

izer  in  this  case^rather  than  as  a solvent. Phenol  was  used  as  a 
, 2 1 
solvent  by  Parr  and  Hadley  ,and  by  Fraser  and  Hoffman, from  which 

conclusions  as  to  the  constitution  of  coal  were  made. However  it  is 

feared  that  phenol  is  more  of  a reagent  than  a solvent. Fischer 

was  probably  the  first  to  do  intensive  work  on  benzene  as  a solvent 

and  came  Jo  the  oonoluslone  of  the  other  worhere  as  regards  the 


3 


constitution  of  coal, These  connclusions  were  that  coal  is  made  up 

of  tv;o  main  constituents, the  cellulosic  and  the  resinic. There  is 

\ 

stillsa  third  constituent  of  which  very  little  is  known, which  is 

3 

termed  the  nitrogenous  part.^rfim  and  Ulbrick  used  benzene  but.  supple 
mented  the  treatment  with  that  of  hydrofluoric  acid  first. This  gave 
a higher  yield  of  extract , probably  due  to  the  removal  of  the  ash 
and  the  benzene  was  able  to  attack  the  soluble  constituents  easier. 
Nothing  can  be  found  in  the  literature  on  the  use  of  xylene  as 
a solvent, but  since  it  is  found  in  both  petroleum  and  coal  tar, it 
should  be  a valuable  solvent  in  this  investigation, This  follows 
from  the  fact  that  sitoilar  solvents  or  substances  should  disolve 
in  one  another  much  easier  than  two  substances  more  distantly 
related. 

Solvents  for  bitumens  and  substances  of  like  nature  have  been 

confined  to  two  classes. The  first  is  used  t4)  seperate  the  two  main 

constituents, called  "asphaltenes"  and  "petroleneB",This  class  of 

solvents  includes  petroleum  ether, benzene, chloroform, and  acetone. 

The  other  class  of  solvents  is  used  for  completly  disolving  the 

material  when  used  in  bituminous  paints, etc. This  class  consists  of 

5 4 

carbon  disulfide  and  turpentine  mainly.Endenmann  in  1696  did  some 
work  on  this  seperation, which  seemed  to  be  an  old  field  then. He 
called  the  material , precipitated  by  petroleum  ether  and  soluble 
in  chloroform, asphaltenes. The  material  soluble  in  petroleum  ether 
was  termed  petrolenes. Carbon  disulfide  is  the  solvent  most  generaljry 
used  to  disolve  the  bituminous  material  for  most  work, and  most 
asphalts  such  as  Gilsonite  and  Grahamite  are  souble  in  all  pro- 
portions. 


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4 


II .Purpose 

The  purpose  of  this  part  of  the  investigation  is  to  find  a 
suitable  solvent  for  the  study  of  the  extract  of  a cannel  coal, 
and  to  ditermine  under  what  conditions  this  extraction  can  be 
carried  out  (to  the  best  advantage. 


5 


III .Experimental 

A,  Description  of  sample. 

The  original  sample  was  from  a peice  of  material  supposed  to 
be  a Kentucky  cannel  coal. The  block  was  very  hard, could  not  be 
sawed  or  chiseled  except  into  small  chips./,  sample  was  finally 
obtained  by  splitting  the  chunk  along  the  grain. The  coal  has  a 
slate  color  before  grinding, but  after  grinding  a brownish  black 
color  was  nottcable. After  going  through  the  coffee  mill  the  wanple 
had  to  be  air  dried  before  grinding  in  the  ball  mi 11, as  the  powder 
was  sticky.This  coal  on  carbonization  is  recorded  as  giving  a 
yield  of  sixty  three  gallons  of  tar  per  ton, which  is  an  extremely 
high  yield. 

B.  Benzene  extraction. 

Benzene  was  first  tried  useing  a Barrett  free  carbon  extraction 
apparatus, with  an  alundum  cup  as  the  filtering  medium. Twenty  grams 
of  the  powdered  sample, which  had  all  passed  through  a hundred  mesh 
seive,was  placed  in  the  cup. Extraction  was  carried  out  for  five 
hours, and  after  allowing  the  cup  to  drain  and  cool, the  extract  was 
poured  out  and  fresh  benzene  added. The  extract  in  the  benzene  was 
fluorescent , green  in  reflected  light, and  red  by  transmitted  light. 
After  another  five  hours  of  extraction, the  extracts  were  united 
and  the  benzene  evaporated  off  at  a temperature  of  eighty  five 
degrees  in  an  electric  furnace , until  no  further  odor  of  benzene 
was  notica-ble.A  third  extraction  of  five  hours  was  found  to  be  use- 
less as  the  benzene  was  scarcely  colored. 

In  order  to  check  the  effeciency  of  the  Barrett  extractor 
twenty  grams  of  coal  were  refluxed  in  an  erlenmeyer  flaskwith 


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6 


benzene  for  three  hours.  This  gave  a smaller  extraction,  probably 
because  of  lack  of  time  and  a.lso  beca.use  the  benzene  may  not  have 
come  in  contact  v/ith  all  of  the  coal. 

Vignon  recommended  the  use  of  hydrflouric  acid  before  ex- 
traction with  the  benzene,  so  tv/enty  grams  of  coal  were  treated 
with  a mixture  of  hydrochloric  acid  and  hydrofluoric  acid  in  a 
parrafin  cup.  Heat  was  developed  which  almost  melted  the  cup, 
showing  that  some  sort  of  a chemical  reaction  was  taking  place, 
but  after  washing  vdth  hot  water  and  drying,  the  coal  failed  to 
give  a much  higher  yield  of  extract. 

Pressure  extraction  was  next  carried  out  in  a mercury  shipp- 
ing cylinder.  This  cylinder  v/s.s  an  iron  container  six  inches  in 
diameter  and  fourteen  inches  in  heighth,  v/ith  a screv/  plug  in  the 
top.  Twenty  grams  of  sajrple  v/ere  -placed  in  the  bomb  and  a liter 
of  benzene  added.  The  plug  was  sealed  in  with  a litharge-glycerol 
mixture  and  the  bomb  heated  to  two  hundred,  and  seventy  five  de- 
grees for  fifty  hours.  This  temperature  v/ould  give  a pressure 
of  about  fifty  atmospheres.  On  filtration  and  washing  the  ex- 
tract v^as  much  darker  in  color  than  any  previous  extraction,  but 
the  coal  still  resembled  the  original  sample  s-lltho  it  had  lost 
some  of  its  original  lustre. 


Table  I 

m .of 
sample 

T^t.  of 
residue 

Ft.  of 
extract 

Percent 

extraction 

Treatment 

20 

19.56 

. 602 

3.01 

Barrett  extractot 

20 

19.67 

.574 

2.67 

Refluxing 

20 

— 

. 680 

3.40 

Treated  with  HP. 

20 

18.27 

1.876 

9,38 

Under  pressue  for 

50  hours. 


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7 


The  sura  of  the  weight  of  the  extract  and  the  residue  did  not  check 
with  the  weight  of  the  coal  treated,  altho  the  residue  was  washed 
v;ith  alcohol  and  ether,  and  dried  at  on  hundred  degrees  for  one 
hour,  and  the  extract  was  dried  at  eighty  five  degrees  vOiich  is 
above  the  boiling  point  of  benzene.  Indicating  that  some  of  the 
benzene  must  have  been  left  in  either  the  extract  or  residue. 

The  extract  in  all  cases  was  tarry,  serai-solid,  and  liquid 
at  the  drying!.:  temperature,  and  could  be  dented  with  a glass  rod 
at  room  temperature. 

C.  Xylene  extraction 

Xylene  was  next  used  in  the  Barrett  extraction  apparatus  in 
a similar  way  to  that  of  the  benzene.  It  was  found  that  six  or 
eight  hours  w^ere  sufficient  to  take  out  all  of  the  extractable 
material  useing  this  method.  The  xylene  extract  v.^as  a much  darker 
solution  than  any  of  the  solutions  obtained  by  the  use  of  benzene, 
showing  that  something  v^as  being  extracted,  which  the  benzene  did 
not  remove. 

A relux  apparatus  v;as  used  to  obtain  a raaxiiiiura  yield  of  ex- 
tract to  use  in  further  tests.  It  was  a suprise  to  find  that  this 
gave  a higher  j'-ield  than  that  given  by  the  Barrett  free  ca,rbon 
apparatus.  This  v/as  probably  due  to  the  fact  that  the  coal  v^as 
in  direct  contact  vdth  the  hot  xylene  instead  of  the  newly  con- 
densed cold  xylene  as  in  the  Barrett  apparatus. 

Pressure  was  the  next  thing  in  order  and  v.^as  carried  out  in 
the  same  manner  as  the  benzene  extraction  except  that  the  temper- 
ature was  raised  to  three  hundred  and  seventy  five  degrees. 

Several  different  runs  were  Made,  and  it  was  found  that  a period 
of  two  days  was  the  best  for  maximum  extraction. 


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8 


The  x;/-lene  v;ns  evaporated  off  in  all  caBee  at  a temperature  of  a 
nteam  bath,  under  a diminished  pressure  of  about  eight  centimeters 
of  mercury. 

Table  II 


Y/t . of  Wt . of  \Tt . of  Percent  Treatment, 
sample  residue  extract . extract 

20  .830  4.15  Barrett  free  carbon 

appctratus . 

100  95.04  5.470  5.47  Refluxing;. 

50  3.485  6.97  Pressure  for  15 

hours . 

50  44.85  6.325  12.65  Pressure  for  50 

hours . 


B.  Ultimate  analysis. 

In  order  to  check  up  on  the  extraction  of  the  coal  an  ulti- 
mate analysis  was  run  on  the  original  coal,  the  extract,  and  the 
residue.  Ca.rbon  v/as  determined  in  a Parr  total  carbon  apparatus, 
and  sulfur  v;as  run  on  the  solution,  after  the  carbon  dioxide  ho,d 
been  determined,  by  gravimetric  determination.  The  b.  t.  u.  v/as 
determined  in  a Parr  oxygen  bomb  calorimeter.  Nitrogen  v/as  de- 
termined by  the  Kjeldahl  method,  hydrogen  by  Bulong's  formula  and 


Oxygen  by  difference. 

Table  III 

Extract  Residue  Coal 


Dry 

Percent 

Dry 

Percent 

Total 

Dry 

Air 

coal 

coal 

dry . 

Yield 
IToist . 

12.65 

87.35 

100 

1.0 

Ash. 

1 

.1  .14 

16.43 

14.35 

14.49 

14.39 

14 . 1 

Carbon 

81 

.8  10.35 

73.1 

63,85 

74.20 

74.84 

74.1 

ITydrog 

en9  . 

74  1.23 

3.61 

3.15 

4.33 

4.30 

4.3 

Ox^'g  en 

4. 

03  . 50 

2.53 

2.21 

2.71 

2.64 

2.6 

Nitrogenl . 

48  .18 

1.56 

1.36 

1.54 

1.32 

1.31 

Sulfur 

1. 

82  . 23 

2.67 

2.33 

2.56 

2.  59 

2.57 

B . t . u . 

17, 

728  2242 

12,876 

11, 246 

13,488 

13, 524 

13,384 

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9 


E.  Discussion  of  results. 

The  results  obtained  in  the  ultimate  analysis  of  the  extract 
and  residue  check  fairly  v:ell  with  those  of  the  original  sainple 
v;ith  the  exception  of  the  carbon.  The  total  carbon  in  the  extract 
and  residue  is  less  than  that  in  the  original  coal.  This  loss  in 
carbon  can  only  be  explained  by  the  fact  that  it  was  extremely  dif 
ficult  to  get  a complete  fusion  of  the  extract.  Also  the  extract 
was  in  such  a state  that  a saraple  had  to  be  weighed  out  on  a piece 
of  glass  and  then  the  glass  and  all  had  to  be  placed  in  the  bomb. 
On  ignition  tlie  glass  fromed  a sodiura  silicate  and  this  floculent 
precipitate  may  have  kept  some  of  the  carbon  dioxide  from  being 
evolved  on  the  addition  of  acid. 

V.  Conclusions. 

1.  The  results  show  Xylene  to  be  a good  solvent,  and  better 
than  benzene  under  pressure,  probably  because  a higher  temperature 
can  be  used  under  the  same  pressure. 

2.  The  ultimate  ana.lysis  shows  that  Xylene  is  a solvent  and  not 
a reagent,  as  no  new  compounds  could  be  formed  and  still  have  the 
ultimate  analysis  check  so  well. 

3.  Nitrogen  and  sulfur  are  about  evenly  distributed  between 
the  extractable  material  and  the  residue. 

4.  From  the  heating  values  the  extract  seems  to  be  the  stronger 
heating  element  of  the  two  const ituents. 


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10 


A Study  of  the  Propertiee  of  the  Extract  Obtained  from  a Canned 
Coal  uneinc  Benzene  a.nd  Xylene  d.s  Solvent n. 

Part  II 


I.  Introduction. 


AmonG  our  great  natural  resources,  coal  and  petroleur.i  are 
among  the  most  important.  Altho  these  tv'O  substances  can  not  be 
classed  together,  there  is  no  doubt  that  some  relation  exists 
bet^veen  the  tv/o.  A comparison  of  the  formation  of  these  tv/o 
final  products  may  show  a closer  relationship. 

Petroleum 

r > 

non-asphalt ic  petroleum  Mineral  base  and  asphaltic  petroleum 

•’  Aspha.lt  s 

( \ 

mineral  v.'axes  Impure  pure  a,nd  fairly  pure 


Graphite 

Prom  this  v/e  see  that  there  is  a substance  forriied  during  the 
formation  of  coal/  and  one  formed  from  the  metamorphisis  of 
asphaltic  petroleum,  v:hich  resemble  each  other  to  a marlced  d^egree. 
Of  course  these  materials  are  not  identical,  since  they  are 


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11 


formed  under' different  conditions  and  from  a-. different ^motherL  sub- 
stance. However  they  have  some  of  the  same  physical  and  chemic:il 
properties. 

II.  ■'historical. 

The  explaination  of  the  formation  of  the  asohaltic  material, 
is  that  it  v/as  formed  during  the  filtration  of  the  mother  liquid, 
thru  a filtering  medium  of  clay  or  roch,  and  the  more  viscous 
asphaltic  material  was  left  behind,  in  the  silicious  matter  to 
form  the  natural  asphalt.  Thus  we  see  that  altho  coal  is  supposed 
to  have  been  deijosited  cont emporaneously  with  the  rocks  and  clay 
material,  the  deposite  of  the  asphalt  material  was  subsequent  to 
that  of  the  rocks. 

Hackford(6)  says  that  the  chief  difference  between  the  so- 
called  coal  and  the  true  coals  rests  in  the  fact  that  the^/  possess 
no  cellulose  residue.  It  is  conceivable  that  a kerite  produced 
from  vegetable  remains,  containing  some  cellulose,  but  not  suf- 
ficient quantities  to  form  a sponge  like  material  necessary  to 
hold  the  oil  in  situ  while  the  decomposition  proceeds,  would  be 
an  intermediate  betv:een  oil  and  coal.  It  is  a substance  of  this 
nature  which  v^e  are  investigating. 

Arne’  Picte(7)  has  done  some  work  on  the  relationship  of  these 
two  substances,  coal  and  petroleum,  and  drav;s  the  conclusion  that 
they  are  of  the  same  origin,  from  the  common  characteristic  shovm 
b;/  the  two  substances.  These  are  the  boiling  point,  density,  and 
index  of  refraction  of  petroleum  and  tar  from  coal.  The  tar  was 
obtained  in  tv:o  different  ways,  either  by  distillation  or  by 
extraction . 

Asphalts  were  knovTi  as  early  as  3000  to  2500  B.C.,  but  were 


M ill  Ml  iiiii ' III  mlitiiiii  in’iir  I mil  Tii  ' ? <i  I 'll'iiflWi  iiiiiii  j||pa  »n'  1*11^ 

■Ttr  ■ 

’ '■  V '* 

• 3*!^  ' ’ ' ■’■•.,■ 

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>'  r » 

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»>Me  A^.''^*i'’  .^li 


1 


[■■  w/'  ■'!,' 

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>■',^,1  m ^ " fjri  ■ sf  T • ■ •'“■  . i’  f.  .*  ‘ 

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12 


not  discovered  in  U.S.  until  1555.  Grahaniite  -was  discovered  in 
V'est  Virginia  in  1863,  and  Gilsonite  in  Utah  in  1885.  All  of  the 
native  asphalts  in  the  state  of  Kentucky,  from  vdiich  the  object 
of  this  investigation  ccrnie,  are  com  osed  of  sand  and  sandstone, 
co.rrying  between  tv;elve  and  fourteen  per  cent  of  soft  asphalts 
in  the  interstices.  The  extracted  asphalts  from  one  of  these 
samples  gave  a penatration  test  of  35  to  45  at  77°!P.  and  yielded 
twelve  per  cent  of  fixed  carbon.  (5) 

Purpose 

To  determine  the  similarity  or  distinction  between  cannel 
coa.1  and  asphalt,  expecia.lly  Gilsonite  and  Grahmite  which  seem  to, 
resemble  the  coal  most  closely. 


13 


Hethodn  of  Invest i/-;:at ion 

In  defininc  a substance  v;e  have  to  rely  on  several  different 
criteria  among  the  most  important  arc  origin,  physical  properties, 
solubility,  and  chemical  properties ( 5 ) . In  the  case  of  asphalt, 
such  as  Gilsonite,  and  a cannel  coal  it  mig/it  be  hard  to  differ- 
entia,te  betv.'een  the  tro  as  far  as  origin  is  concerned.  The  in- 
dications rs  to  the  origin  are  most  likely  to  be  confusing  since 
many  geological  obstacles  may  be  met.  But  considering  the  other 
factors,  physical  properties,  chemical  properties,  a,nd  solubility, 
ive  c.an  come  closer  to  the  truth.  From  these  v/e  can  Sc.y  that 
a.sphalt,  Gilsomite  in  this  case  is  a species  of  bitumen,  including 
dark  colored  conpa.ritively  Htird  and  non- vola.tile  solids;  composed 
of  hj”- dr 0 carbons,  substancialy  free  from  oxygenated  bodies  and 
crj^stallized  paraffins;  some  times  associated  vdth  mineral  matter, 
the  non-mineral  constituents  being  difficultly  fusible  and  largly 
soluble  in  carbon  disulfide,  - and  v/hose  distillate  fractioned  be- 
tween 300°-350'^C.  yields  considerable  sulfonation  residue(5). 

■ViThile  on  the  other  hand  a coa,l  might  be  defined  as  a degradation 
product  of  Tegeta,ble  remains  composed  of  hy droca,rbons  containing 
a fairly  large  amount  of  parraffins  and  a.bout  the  same  amount 
of  minera.l  natter  as  the  a.sphalt  contains.  Altho  cannel  coa.l 
vill  burn  on  lighting  vith  a natch  it  does  so  with  out  fuseing, 
and  is  not  very  soluble  in  carbon  di-sulfide.  On  heating  it  gives 
off  a large  amount  of  volatile  ma.tter,  sometimes  as  much  as 

Bitumens  ;vere  knovm  to  yield  a part  of  their  constituents  to 
a certain  class  of  solvents  a.nd  another  constituent  to  another 
class  of  solvents  by  Boussinggault  in  1857(6).  Today  v/e  detemnine 
o.sphaltines  a.s  that  portion  insoluble  in  petroleum  ether,  but 


T.  ' 


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14 


F-oluMe  in  l^enr^ene,  ?.s  a direct  application  of  this  principal. 
Asphaltenes  and  their  parent  substance  asphaltic  resins  care  re- 
garded cas  saturated  polycyclic  compounds  containing  Sulphur  or  Ox- 
ygen either  of  which  c...n  replace  the  other(5).  This  asphaltene 
test  can  he  employed  for  the  purpose  of  identification,  p^s  mineral 
v;axes,  peat-,  lignite-,  and  shale  tars  or  pitches  s.re  largely  sol- 
uble in  petroleum  ether, while  native  and  petroleufla  asphalts  are  're- 
latively in  soluble,  depending  on  their  previous  treatment. 

Ai-nong  the  physicp.1  properties  that  can  be  used  are  'specific 
gravity,  melting  point,  color,  streak,  hardness,  fracture,  and 
ductility.  Some  of  tests  are  common  to  both;  but  the  specific 
gravity  of  Gilsonite  is  less  than  that  of  the  ordinary  coal;  The 
melting  or  fusing  point  of  asphalt  is  veil  defined  while  cannel 
coal  is  infusible.  :^Both  ha^-e  a concoidal  fracture,  mid  the  color 
mid  streak  might  be  the  sr.me. 

In  the  chemical  properties  the  ultimate  analysis  is  very  im- 
portant, also  ash,  fixed  carbon,  free  Ccarbon,  and  water  may  be 
determining  factors.  A cannel  coal  contains  about  77-78/^  conbon, 
11-12^  Hydrogen,  and  less  than  \%  nitrogen  and  Sulfur,  and  about 
9/'  Oxygen.  TTnile  Gilsonite  gives  an  analysis  of  carbon 
Hydrogen  8-10^,  Sulfur  1.7- 2.0?^,  Hitrogen  less  than  1%,  Oxygen  up 
to  2^.  Cannel  coal  has  a fixed  carbon  of  7-8<  Y.'hile  Gilsonite 

has  from  10-20^  (5). 


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15 


Experimental  on  the  extr.'',ct. 

(1)  Physical  properties. 

The  extract  was  a stichy  ginmy  substance,  black  in  color  and 
had  a (Glassy  lustre.  The  odor  was  that  simil''r  to  tar. 

The  specific  gravity  was  deterrained  by  weighing  in  air  and 
water  and  proved  to  be  very  close  to  that  of  v/ater.  The  inateria.1 
when  made  into  a ball  and  suspended  in  a hot  air  bath  melted  at 
82°C.  and  had  a flash  point  of  160*^0.  On  heating  in  a dish  the 
ball  melted  suddenly  and  flowed  readily. 

( 2 ) Chem i c al  properties. 

Paraffins  determine  the  characteristic  of  a tar,  and  were  run 
by  the  sulfonation  method.  The  extract  was  disolved  in  bensene 
and  treated  v/ith  fuming  suluric  acid,  and  heated  for  one  hour  <at 
lOO^C,  shaking  at  intervals.  The  liquid  was  then  washed  into  a 
Eabcock  bottle  v;ith  concentrated  sulfuric  acid  and  cetrifuged  after 
one  cubic  centimeter  of  gasoline  had  been  added.  As  no  increase 
of  the  volume  of  the  gasoline  could  be  noted  the  gasoline  wa.s  re- 
moved with  a pipette  and  evaporated  to  dryness.  A very  small 
amount,  .1%  was  found.  A blank  was  run  on  both  the  gasoline  and 
benzene  and  the  arnount  in  the'm  v;as  negigible. 

Asphaltenes  were  determined  by  the  method  of  Hamor  and  Pagett, 
a,nd  gave  a yield  of  38.5/^.  The  asphaltic  material  on  evaporating 
off  the  benzene  v/as  a black  solid,  \vhich  cracked  off  the  bottom 
of  the  beolcer  easily,  and  somewhat  resembled  the  shiny  parts  of 
coal . 

Iodine  number  run  xrith  a Hanus  solution  according  to  the 
method  outlined  by  Cherry  sho:ve  ' the  coal  to  be  unsaturated  but 
the  extract  v;as  not. 


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16 


Pree  carbon  according  to  the  Hajnor  (Sc.  Pjigett  method  proved  to 
be  almost  negigible,  beinc  only  ,2Z%. 

(3)  Solubility, 

A1  tho  the  Xylene  took  out  ?nore  extract  than  the  benzene  the 
xylene  extract  v;as  entirely  soluble  in  benzene. 

The  extract  was  also  97.5  percent  soluble  in  ca^rbon  disulfide 
and  7S.5  percent  soluble  in  carbon  disulfide  ether. 

Conclusion  to  tests:- 

The  chemical  tests  show  that  the  material  must  have  been 
formed  from  an  asphaltic  base,  and  that  the  degree  of  unsaturation 
of  the  extract  is  very  lov;. 

The  physical  tests  show  the  extract  closely  resembles  natural 
asphalts,  al  tho  all  of  the  temperatures  are  a little  lower. 

This  is  possi'^'le  since  the  extract  contains  none  of  the  higher 
boiling  constituent  that  are  present  in  the  natural  asphalt.  Also 
there  is  no  ash  in  the  extract  as  there  is  in  the  natural  product 
v^hich  should  keep  the  material  from  melting  at  such  a low  temper- 
ature. 

The  soulubility  tests  resemble  those  of  a natural  asphalt 
very  much.  Follov;ing  is  a comparison  of  the  extract  which  with 
several  natural  asphalts:- 


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17 


Extract 

Gilsonite 

Grahainite 

Lignite 

Eass  color 

tar  pitch 

Black 

black 

black 

black 

Lustre 

bright 

bright 

bright 

dull 

Sp.  gr. 

1.005 

1.05-1.1 

111.-1.2 

1.05-1.2 

Fussing  point 

82°C 

llOOG 

180O 

up  to  110° 

Mineral  mat. 

1 

up  to  5 

up  to  1 

1 

Solubility ; - 

Fenzene 

all 

71 

largely'' 

CS2 

97.5 

all 

45-100 

95-99 

Ethyl  ether 

75.5 

all 

Paraffin  scale 

.08 

trace 

great 

5 

C 

82.7 

n 30 

37 

H 

9.7 

8.5-10 

8 

S 

1.5 

1.7-2 

1.8 

.5-1.5 

0 

4 

2 

5.10 

Conclusions 

1.  The  extract  had  a low  degree  of  unsaturation . 

2.  The  soluhility  of  the  extract  resembles  that  of  asphalts. 

3.  The  physical  properties  resemble  those  of  asphalts. 


18 


Conclusions 

(1)  investigation  show  that  in  reality,  a cannel  coal 
should  not  he  classed  as  a coal,  hut  more  as  a variety  of 
natural  asphalts. 

(2)  Xylene  is  a good  solvent  for  the  asphaltic  constituent 
of  coal. 

(3)  There  is  a possibility  of  obtaining  a valuable  asphaltic 
constituent  from  cannel  coal  by  extraction  if  a suitable 
cheap  solvent  can  be  found.  The  use  of  some  petroleum 
product  might  be  invest igat ed. 


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Bibliography 


1. Wm.A.Bone.Coal  and  Its  sclentlfio  uses. 

2,  Parr  and  Hadley, Uni v, of  111.  B'iHsttln  No.'J'B. 

5. Grftn  and  Ulbrick.  Chem.abs,  j;  744, 

4.H.Endenmann. J.S.C.I . 15:871>S76. 

Abraham. Asphalts  and  allied  substances. 

6.  J.E.Haokford. Nature  of  coal.  Min. and  Met.  163 ; 35. 

7. Ak4  PlotAt.  Ann.Chemle,  10;349i-330. 

8.  White  and  Thelssen.The  origon  of  coal. B. of  K.B'.jI.No.SS. 


